I will test it right now on my freshly wiped/patched VMware XP box. Will edit this post and return with results momentarily! :-)
--Results--
Well, I'm not sure If I'm not following your instructions right or something else... when I add a default route to a non used IP there is no problems. After I added the route I went to internet explorer typed in www.google.com and it pulled up just fine. So, I wondered why this could be? Here is my routing table
Active Routes:
Network Destination Netmask Gateway Interface Metric
0.0.0.0 0.0.0.0 192.168.1.1 192.168.1.8 10
0.0.0.0 0.0.0.0 192.168.1.90 192.168.1.8 1
127.0.0.0 255.0.0.0 127.0.0.1 127.0.0.1 1
192.168.1.0 255.255.255.128 192.168.1.8 192.168.1.8 10
192.168.1.8 255.255.255.255 127.0.0.1 127.0.0.1 10
192.168.1.255 255.255.255.255 192.168.1.8 192.168.1.8 10
224.0.0.0 240.0.0.0 192.168.1.8 192.168.1.8 10
255.255.255.255 255.255.255.255 192.168.1.8 192.168.1.8 1
Default Gateway: 192.168.1.1
===========================================================================
Persistent Routes:
Network Address Netmask Gateway Address Metric
0.0.0.0 0.0.0.0 192.168.1.90 1
See the reason I believe why this isn't working, is that with Windows the DEFAULT GATEWAY is specified outside of the routing table, unlike linux. So even with this default route in, as you can see it STILL has the default gateway located right above the line of =====================
Default gateway could be changed, however if the users are dynamically assigned an IP, they will also be assigned a DG. If you wanted to change their default gateway you would have to swtich them to a static IP... and at that rate your probably better off doing one of the methods previously described!
Interesting note was, after I had changed my routing table, and then was going to test to see if the entry was deleted by using the 'Repair' option in the Adapter Details, it dropped my regular default gateway and instead the 192.168.1.90 (un used) address was applied. So really this is a great idea you guys thought of, for people who want to disallow network access. Just add the default route to your routing table, then run the repair option on your ethernet adapter. the only downside is with this method NO network functions will work, the packets are directed at a non-existant gateway, thend ropped. Also another concern is that if the IP is assigned via DHCP, you may have to worry about the DHCP assigned default gateway over-writing the one in the routing table. Anyways good work :-p